Carrier multiplication yields in CdSe and CdTe nanocrystals by transient photoluminescence

Engineering semiconductors to enhance carrier multiplication (CM) could lead to increased photovoltaic cell performance and a significant widening of the materials range suitable for future solar technologies. Semiconductor nanocrystals (NCs) have been proposed as a favourable structure for CM enhancement, and recent measurements by transient absorption have shown evidence for highly efficient CM in lead chalcogenide and CdSe NCs. We report here an assessment of CM yields in CdSe and CdTe NCs by a quantitative analysis of biexciton and exciton signatures in transient photoluminescence decays. Although the technique is particularly sensitive due to enhanced biexciton radiative rates relative to the exciton, kradBX > 2 kradX, we find no evidence for CM in CdSe and CdTe NCs up to photon energies E > 3 Eg, well above previously reported relative energy thresholds.Comment: 9 pages, 6 figure

Final Report for DE-FG36-08GO18007 "All-Inorganic, Efficient Photovoltaic Solid State Devices Utilizing Semiconducting Colloidal Nanocrystal Quantum Dots"

We demonstrated robust colloidal quantum dot (QD) photovoltaics with high internal quantum efficiencies. In our structures, device durability is derived from use of all-inorganic atmospherically-stable semiconducting metal-oxide films together with QD photoreceptors. We have shown that both QD and metal-oxide semiconducting films and contacts are amenable to room temperature processing under minimal vacuum conditions, enabling large area processing of PV structures of high internal efficiency. We generated the state of the art devices with power conversion efficiency of more than 4%, and have shown that efficiencies as high as 9% are achievable in the near-term, and as high as 17% in the long-term

Morphology of passivating organic ligands around a nanocrystal

Semiconductor nanocrystals are a promising class of materials for a variety of novel optoelectronic devices, since many of their properties, such as the electronic gap and conductivity, can be controlled. Much of this control is achieved via the organic ligand shell, through control of the size of the nanocrystal and the distance to other objects. We here simulate ligand-coated CdSe nanocrystals using atomistic molecular dynamics, allowing for the resolution of novel structural details about the ligand shell. We show that the ligands on the surface can lie flat to form a highly anisotropic 'wet hair' layer as opposed to the 'spiky ball' appearance typically considered. We discuss how this can give rise to a dot-to-dot packing distance of one ligand length since the thickness of the ligand shell is reduced to approximately one-half of the ligand length for the system sizes considered here; these distances imply that energy and charge transfer rates between dots and nearby objects will be enhanced due to the thinner than expected ligand shell. Our model predicts a non-linear scaling of ligand shell thickness as the ligands transition from 'spiky' to 'wet hair'. We verify this scaling using TEM on a PbS nanoarray, confirming that this theory gives a qualitatively correct picture of the ligand shell thickness of colloidal quantum dots.Comment: 17 Pages, 9 Figure

Revealing single emitter spectral dynamics from intensity correlations in an ensemble fluorescence spectrum

We show that the single emitter linewidth underlying a broadened ensemble emission spectrum can be extracted from correlations among the stochastic intensity fluctuations in the ensemble spectrum. Spectral correlations can be observed at high temporal and spectral resolutions with a cross-correlated pair of avalanche photodiodes placed at the outputs of a scanning Michelson interferometer. As illustrated with simulations in conjunction with Fluorescence Correlation Spectroscopy, our approach overcomes ensemble and temporal inhomogeneous broadening to provide single emitter linewidths, even for emitters under weak, continuous, broadband excitation.Comment: 9 pages, 5 figure

A Low Reabsorbing Luminescent Solar Concentrator Employing π-Conjugated Polymers

A highly efficient thin-film luminescent solar concentrator (LSC) utilizing two π-conjugated polymers as antennae for small amounts of the valued perylene bisimide Lumogen F Red 305 is presented. The LSC exhibits high photoluminescence quantum yield, low reabsorption, and relatively low refractive indices for waveguide matching. A Monte Carlo simulation predicts the LSC to possess exceptionally high optical efficiencies on large scales.National Science Foundation (U.S.) (Graduate Research Fellowship Program (Grant No. 1122374))Eni S.p.A. (Firm) (Eni-MIT Solar Frontiers Alliance

Carrier multiplication yields in PbS and PbSe nanocrystals measured by transient photoluminescence

We report here an assessment of carrier multiplication (CM) yields in PbSe and PbS nanocrystals (NCs) by a quantitative analysis of biexciton and exciton dynamics in transient photoluminescence decays. Interest in CM, the generation of more than one electron and hole in a semiconductor after absorption of one photon, has renewed in recent years because of reports suggesting greatly increased efficiencies in nanocrystalline materials compared to the bulk form, in which CM was otherwise too weak to be of consequence in photovoltaic energy conversion devices. In our PbSe and PbS NC samples, however, we estimate using transient photoluminescence that at most 0.25 additional e-h pairs are generated per photon even at energies hv > 5Eg, instead of the much higher values reported in the literature. We argue by comparing NC CM estimates and reported bulk values on an absolute energy basis, which we justify as appropriate on physical grounds, that the data reported thus far are inconclusive with respect to the importance of nanoscale-specific phenomena in the CM process.Comment: 10 pages, 7 figure

Improved performance and stability in quantum dot solar cells through band alignment engineering

Solution processing is a promising route for the realization of low-cost, large-area, flexible and lightweight photovoltaic devices with short energy payback time and high specific power. However, solar cells based on solution-processed organic, inorganic and hybrid materials reported thus far generally suffer from poor air stability, require an inert-atmosphere processing environment or necessitate high-temperature processing [superscript 1], all of which increase manufacturing complexities and costs. Simultaneously fulfilling the goals of high efficiency, low-temperature fabrication conditions and good atmospheric stability remains a major technical challenge, which may be addressed, as we demonstrate here, with the development of room-temperature solution-processed ​[ZnO over ​PbS] quantum dot solar cells. By engineering the band alignment of the quantum dot layers through the use of different ligand treatments, a certified efficiency of 8.55% has been reached. Furthermore, the performance of unencapsulated devices remains unchanged for over 150 days of storage in air. This material system introduces a new approach towards the goal of high-performance air-stable solar cells compatible with simple solution processes and deposition on flexible substrates.National Science Foundation (U.S.)Hertz FoundationSamsung Advanced Institute of TechnologyNational Institutes of Health (U.S.) (Massachusetts Institute of Technology. Laser Biomedical Research Center. Contract 9-P41-EB015871-26A1)National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (MIT Center for Materials Science and Engineering. Award DMR-08-19762

Objective, comparative assessment of the penetration depth of temporal-focusing microscopy for imaging various organs

Temporal focusing is a technique for performing axially resolved widefield multiphoton microscopy with a large field of view. Despite significant advantages over conventional point-scanning multiphoton microscopy in terms of imaging speed, the need to collect the whole image simultaneously means that it is expected to achieve a lower penetration depth in common biological samples compared to point-scanning. We assess the penetration depth using a rigorous objective criterion based on the modulation transfer function, comparing it to point-scanning multiphoton microscopy. Measurements are performed in a variety of mouse organs in order to provide practical guidance as to the achievable penetration depth for both imaging techniques. It is found that two-photon scanning microscopy has approximately twice the penetration depth of temporal-focusing microscopy, and that penetration depth is organ-specific; the heart has the lowest penetration depth, followed by the liver, lungs, and kidneys, then the spleen, and finally white adipose tissue.National Institutes of Health (U.S.) (NIH-5-P41-EB015871-27)National Institutes of Health (U.S.) (DP3-DK101024 01)National Institutes of Health (U.S.) (1-U01-NS090438-01)National Institutes of Health (U.S.) (1-R01-EY017656 -0,6A1)National Institutes of Health (U.S.) (1-R01-HL121386-01A1)National Institutes of Health (U.S.) (NIH 5U54 CA151884-04)National Institutes of Health (U.S.) (9-P41-EB015871-26A1